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EP0378336B1 - Naphthalocyaninderivate, deren Herstellung, optisches Wiedergabe-Medium mit solchen Verbindungen und dessen Herstellung - Google Patents

Naphthalocyaninderivate, deren Herstellung, optisches Wiedergabe-Medium mit solchen Verbindungen und dessen Herstellung Download PDF

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EP0378336B1
EP0378336B1 EP90300185A EP90300185A EP0378336B1 EP 0378336 B1 EP0378336 B1 EP 0378336B1 EP 90300185 A EP90300185 A EP 90300185A EP 90300185 A EP90300185 A EP 90300185A EP 0378336 B1 EP0378336 B1 EP 0378336B1
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Prior art keywords
formula
naphthalocyanine
compound
spectrum
compound according
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French (fr)
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EP0378336A1 (de
Inventor
Seiji Tai
Nobuyuki Hayashi
Koichi Kamijima
Takayuki Akimoto
Mitsuo Katayose
Hideo Hagiwara
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Resonac Corp
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Hitachi Chemical Co Ltd
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/246—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes
    • G11B7/248—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing dyes porphines; azaporphines, e.g. phthalocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/045—Special non-pigmentary uses, e.g. catalyst, photosensitisers of phthalocyanine dyes or pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/146—Laser beam
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/165—Thermal imaging composition

Definitions

  • This invention relates to a naphthalocyanine derivative, a process for producing the same, an optical recording medium using the same, and a process for producing said optical recording medium.
  • cyanine dyes As organic dyes which absorb near infrared rays, cyanine dyes have heretofore been well known, and metal complexes of oximes and thiols and aminated quinone derivatives are also known as dyes absorbing near infrared rays (Yuki Gosei Kagaku Kyokai Shi, vol. 43, page 334 (1985); Shikizai Kyokai Shi, vol. 53, page 197 (1980); Shikizai Kyokai Shi, vol. 58, page 220 (1985).
  • the cyanine dyes have a very low fastness to light, and hence their use has many restrictions.
  • the metal complexes of oximes and thiols are disadvantageous in that the metals are released from the complexes in a certain medium, as the result of which their ability to absorb near infrared rays is lost.
  • the aminated quinone derivatives are disadvantageous in that they are very poor in the ability to absorb near infrared rays.
  • naphthalocyanine derivatives have been disclosed recently.
  • conventional unsubstituted metal naphthalocyanines Zhurnal Obshchei Khimii, vol. 39, p. 2554 (1969) and Mol. Cryst. Lig. Cryst. vol, 112, p. 345 (1984)
  • Mol. Cryst. Lig. Cryst. vol, 112, p. 345 (1984) are insoluble in organic solvents and hence are very difficult to purify.
  • Recently, synthesis of naphthalocyanine derivatives soluble in organic solvents has been reported (Japanese Patent Application Kokai (Laid-Open) Nos. 60-23451, 60-184565, 61-215662 and 61-215663).
  • these naphthalocyanine derivatives have the following disadvantage. That is, although they are generally soluble in aromatic hydrocarbon solvents and halogen-containing solvents, their solubility in saturated hydrocarbon type solvents is quite low, and hence their organic film cannot directly be formed on polymethyl methacrylate and polycarbonate substrates by wet coating process unless a protecting layer is provided on these substrates. Thus, it has been desired to develop a naphthalocyanine compound having an excellent solubility in saturated hydrocarbon type solvents.
  • Reaction Scheme II (line 3, right upper section, page 8) of Japanese Patent Application Kokai (Laid-Open) No. 61-177288 is a nucleophilic reaction of naphthalocyanine ring resembling Friedel-Crafts reaction and not suitable for introduction of alkoxyl group, alkylthio group and amino group.
  • reaction Scheme III (line 5, right upper section, page 8) of Japanese Patent Application Kokai (Laid-Open) No. 61-177288, the starting compound cannot be purified and the product is a very complicated mixture difficult to purify, so that this reaction is unsuitable for isolation of high purity product. Further, the reaction itself is disturbed by the influence of hydroxyl group attached to Si of starting compound, and the reaction cannot be advanced toward the intended direction.
  • This invention provides a naphthalocyanine derivative represented by the formula (I) below.
  • EP-A-0 296876 describes similar naphthalocyanine dyes having peripheral alkylmercapto groups whereas EP-A-0 279 501 describes naphthalocyanine dyes having peripheral silyl groups SiR3 where R is alkyl or aryl.
  • the present compounds have peripheral silyl alkylmercapto groups and are represented by formula (I): wherein R1 in number of (k + l + m + n) represents identical or different substituent represented by -(CR2R3) x SiR4R5R6; R2, R3, R4, R5 and R6, identical or different one another, represent hydrogen atom, halogen atom, alkyl group, alkoxyl group, aryl group or aryloxyl group; k, l, m and n, identical or different one another, represent an integer of 0 to 4, provided that (k + l + m + n) is 1 or greater; x represents an integer of 1 to 30, provided that the CR2R3 groups, in number of x, may be identical or different; M represents Si, Ge or Sn; and Y represents aryloxyl group, alkoxyl group, trialkylsiloxyl group, triarylsiloxyl group, trialkoxysiloxyl group, triaryloxysil
  • This invention further provides a process for producing naphthalocyanine derivatives represented by the formula (I), an optical recording medium using said naphthalocyanine derivative, and a process for producing said optical recording medium.
  • Figure 1 is IR spectrum of 3,4-bis(dibromomethyl)bromobenzene
  • Figure 2 is NMR spectrum of 6-bromo-2,3-dicyanonaphthalene
  • Figure 3 is IR spectrum of 6-bromo-2,3-dicyanonaphthalene
  • Figure 4 is IR spectrum of 6-bromo-1,3-diiminobenz(f)isoindoline (KBr method)
  • Figure 5 is IR spectrum of dichlorosilicontetrabromonaphthalocyanine (KBr method)
  • Figure 6 is electronic spectrum of dichlorosilicon-tetrabromonaphthalocyanine (tetrahydrofuran solution)
  • Figure 7 is IR spectrum of dihydroxysilicon-tetrabromonaphthalocyanine (KBr method)
  • Figure 8 is electronic spectrum of dihydroxysilicontetrabromonaphthalocyanine (tetrahydrofuran solution)
  • Figure 9 is NMR spectrum of bis(tri-n-propyl
  • naphthalocyanine derivatives represented by formula (I) are excellent in the solubility in saturated hydrocarbon type solvents and they are soluble in aromatic, halogen-containing, ether type and ketone type solvents, too, they can be purified and their purity can be improved easily. Further, their absorption does not change depending on kind of solvent and concentration, and they are quite excellent in the ability to absorb semiconductor laser beams. Further, there is a tendency that these naphthalocyanine compounds having a silicon atom-containing branched chain alkyl group are higher in melting point than the naphthalocyanine compounds having a straight chain alkyl group comparable in the number of carbon atoms, owing to which they are more improved in the stability to reproduce laser beams.
  • Such a stability to reproducing laser beams is affected by melting point of compound, and a compound having a higher melting point is generally higher in the stability to reproducing laser beams. Further, an amorphous film prepared by spin-coating these naphthalocyanine derivatives having a relatively high melting point on an appropriate substrate shows no crystallization of film when allowed to stand under a high temperature-high humidity environmental test condition (80°C, 90% RH), and exhibits an excellent durability.
  • saturated hydrocarbon type solvent hexane, heptane, octane, nonane, decane, undecane, dodecane and the like
  • naphthalocyanine derivatives represented by formula (I) exhibit a particularly high solubility in alicyclic solvents such as cyclopentane, cyclohexane, cycloheptane and the like.
  • Examples of said aromatic solvent include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trimethylbenzene, 1-chloronaphthalene, quinoline and the like.
  • Examples of said halogen-containing solvent include methylene chloride, carbon tetrachloride, trichloroethane and the like.
  • Examples of said ether type solvent include diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether and the like.
  • Examples of said ketone type solvent include acetone, methyl ethyl ketone, methyl propyl ketone, cyclopentanone, cyclohexanone, acetone alcohol and the like.
  • R2, R3, R4, R5 and R6 constituting substituent R1 in formula (I) the followings can be referred to: straight and branched chain alkyl groups such as methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, t-butyl, n-amyl, t-amyl, 2-amyl, 3-amyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl and the like; alicyclic alkyl groups such as cyclohexyl, cyclopentyl, cyclopropyl and the like; alkoxyl groups such as methoxyl, ethoxyl, propoxyl, butoxyl, amyloxyl and the like; aryl groups such
  • Si, Ge and Sn can be referred to.
  • Y the followings can be referred to: aryloxyl groups such as phenoxyl, tolyloxyl, anisyloxyl; alkoxyl groups such as amyloxyl, hexyloxyl, octyloxyl, decyloxyl, dodecyloxyl, tetradecyloxyl, hexadecyloxyl, octadecyloxyl, eicosyloxyl, docosyloxyl and the like; trialkylsiloxyl groups such as trimethylsiloxyl, triethylsiloxyl, tripropylsiloxyl, tributylsiloxyl and the like; triarylsiloxyl groups such as triphenylsiloxyl, trianisylsiloxyl, tritolylsiloxyl and the like; trialkoxysiloxyl groups such as
  • alkyl chain length of Y can be changed in accordance with the oscillating wavelength of the used laser.
  • the shape of the sulfur-containing substituent R1 has a function of controlling solubility of the compound in organic solvent and its melting point, when alkyl chain length of Y is changed.
  • Y is a trialkylsiloxyl group
  • its alkyl chain length exercises a great influence on the spectra of spin-coated film, in such a manner that maximum absorption, minum transmittance and maximum reflectance all shift greatly to the longer wavelength direction when alkyl chain length is shorter.
  • a compound particularly desirable in the point of maximum reflectance with regard to the used semiconductor laser can be selected by changing the alkyl chain length of trialkylsiloxyl group, and R1 can be selected appropriately so as to give optimum solubility and melting point to the naphthalocyanine derivative.
  • Naphthalocyanine derivatives of the formula (I) wherein M is Si or Ge are preferable in this invention.
  • Naphthalocyanine derivatives of formula (I) wherein k, l, m and n are all equal to 1 are preferable in this invention.
  • Naphthalocyanine derivatives of the formula (I) wherein the two symbols Y both represent a trialkylsiloxyl group are preferable in this invention.
  • Naphthalocyanine derivatives of the formula (I) wherein x in the definition of R1 is 1 to 5, particularly 1 to 3, are preferable in this invention.
  • Naphthalocyanine derivatives of the formula (I) wherein R2 and R3 are hydrogen atoms are preferable in this invention.
  • Naphthalocyanine derivatives of the formula (I) wherein R4, R5 and R6 are straight-chain alkyl groups, respectively, are preferable in this invention.
  • Me, Et, Pr, Bu and Ph represent CH3, C2H5, C3H7, C4H9 and C6H5, respectively.
  • naphthalocyanine derivatives of formula (I) can be produced in the following manner. That is, they can be produced by reacting a naphthalocyanine derivative represented by the formula (II): wherein k, l, m, n, R1 and M are as defined in formula (I), with a chlorosilane represented by the formula (III): (R7)3SiCl (III) or a silanol represented by the formula (IV): (R8)3SiOH (IV) provided that, in the formulas (III) and (IV), R7 and R8 independently represent alkyl group, aryl group, alkoxyl group or aryloxyl group, or an alcohol represented by the formula (V): R9OH (V) wherein R9 represents alkyl group or aryl group, or a compound represented by the formula (VI): R10CO ⁇ X (VI) wherein R10 represents alkyl group and X represents a halogen atom, hydroxyl group or acyl
  • a naphthalocyanine derivative represented by the formula (I) can be produced by reacting, at an elevated temp., a compound represented by the formula (II) with an excessive quantity of a compound represented by the formula (III), (IV), (V) or (VI).
  • the reaction temperature is preferably 80-250°C, and the reaction time is preferably 30 minutes to 10 hours.
  • This reaction is preferably carried out in the absence of a solvent or in a solvent such as benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, ⁇ -picoline, quinoline or the like, and optionally in the presence of an aliphatic amine such as triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine and the like.
  • a solvent such as benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, ⁇ -picoline, quinoline or the like, and optionally in the presence of an aliphatic amine such as triethy
  • the naphthalocyanine derivative of the formula (I) can be isolated from reaction mixture and purified by separating the reaction mixture by chromatography and recrystallizing the product, for example.
  • the naphthalocyanine derivative represented by formula (II) can be obtained by hydrolyzing, at an elevated temperature, a naphthalocyanine derivative represented by the formula (IX): wherein k, l, m, n, M and R1 are as defined in formula (I) and X represents halogen atom, provided that the two symbols X may be identical or different each other.
  • the reaction temperature is preferably 50-150°C, and the reaction time is preferably 30 minutes to 10 hours.
  • this reaction is preferably carried out in a solvent mixture such as pyridine/water, pyridine/aqueous ammonia, methanol/aqueous ammonia, ethanol/aqueous ammonia, propanol/aqueous ammonia, and the like.
  • a solvent mixture such as pyridine/water, pyridine/aqueous ammonia, methanol/aqueous ammonia, ethanol/aqueous ammonia, propanol/aqueous ammonia, and the like.
  • the naphthalocyanine derivative represented by the formula (IX) can be obtained by reacting, at an elevated temperature, one mole of 1,3-diiminobenz(f)-isoindoline represented by the formula (X): or one mole of 2,3-dicyanonaphthalene represented by the formula (XI): provided that, in formulas (X) and (XI), R1 is as defined in formula (I) and n represents an integer of 1-4, with 1 to 100 moles of a metal halide represented by formula (XII): MX p (XII) wherein X represents halogen atom, p is a positive integer representing the number of X atoms linked to metal M, and M is Si, Ge or Sn.
  • the reaction temperature of this reaction is preferably 150-300°C, and its reaction time is preferably 30 minutes to 10 hours.
  • This reaction may be carried out either in the absence of solvent or in a solvent such as urea, tetralin, quinoline, 1-chloronaphthalene, 1-bromonaphthalene, trimethylbenzene, dichlorobenzene, trichlorobenzene or the like.
  • This reaction is preferably carried out in the presence of an amine.
  • the amines which can be used for this purpose include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, and the like.
  • As said metal halide, SiCl4, SiBr4, SiI4, GeCl4, GeBr4, SnCl2, SnI2 and the like can be referred to.
  • the 1,3-diiminobenz(f)isoindoline represented by formula (X) can be obtained by heating, under reflux, a 2,3-dicyanonaphthalene derivative represented by formula (XI) for 1-10 hours in methanol in the presence of sodium methoxide catalyst while bubbling ammonia gas.
  • the 2,3-dicyanonaphthalene derivative represented by formula (XI) can be produced mainly by the following two methods.
  • an o-oxylene derivative represented by formula (XIII): wherein R1 is as defined in formula (I) and n represents an integer of 1-4, and N-bromosuccinimide represented by formula (XIV): are irradiated with light at an elevated temperature to obtain a compound represented by formula (XV): wherein R1 is as defined in formula (I) and n represents an integer of 1-4, and then the latter is reacted at an elevated temperature with fumaronitrile represented by formula (XVI): to obtain a 2,3-dicyanonaphthalene derivative represented by formula (XI).
  • the reaction between the o-xylene derivative of formula (XIII) and N-bromo-succinimide of formula (XIV) can be performed by heating, under reflux, 0.2 mole of o-xylene derivative and 0.8 mole of N-bromosuccinimide for 4-12 hours in a solvent inert to irradiation while irradiating the mixture with a high pressure mercury lamp.
  • a peroxide which is a radical generator must be added as a photo reaction initiator.
  • peroxide benzoyl peroxide, octanoyl peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide and the like
  • peroxide is used in an amount ranging from 500 mg to 2 g per 500 ml of solvent.
  • solvent inert to irradiation is appropriately selected from halogen-containing solvents such as chloroform, carbon tetrachloride and the like or aromatic solvents such as benzene, chlorobenzene and the like.
  • the reaction between the compound represented by formula (XV) and fumaronitrile represented by formula (XVI) is carried out by reacting 1 mole of compound (XV) with 1-2 moles of fumaronitrile.
  • the reaction temperature is preferably 70-100°C, and the reaction time is preferably 5-10 hours.
  • polar organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N,N-diethylformamide, N,N-diethylacetamide and the like are preferable.
  • the reaction temperature is preferably 80-250°C, and the reaction time is preferably 1-30 hours.
  • benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, ⁇ -picoline, quinoline and the like can be used either as a single solvent or as a solvent mixture.
  • the bromo-2,3-dicyanonaphthalene represented by formula (XVII) can be synthesized, for example, according to the following Scheme (A) with reference to the description of Zhurnal Organicheskoi Khimii, vol. 7, page 369 (1971):
  • bromo-o-xylene (XVIII) and N-bromo-succinimide represented by formula (XIV): are irradiated with light at an elevated temperature to obtain bis(dibromomethyl)bromobenzene (XIX), and the latter is reacted at an elevated temperature with fumaronitrile represented by formula (XVI): to obtain bromo-2,3-dicyanonaphthalene represented by formula (XVII).
  • the reaction between bromo-o-xylene (XIII) and N-bromosuccinimide (XIV) can be performed by heating, under reflux, 0.2 mole of bromo-o-xylene and 0.8 mole of N-bromosuccinimide for 4-12 hours in a solvent inert to irradiation, while irradiating the mixture with a high pressure mercury lamp.
  • a peroxide which is a radical generator must be added as a photo reaction initiator.
  • peroxide benzoyl peroxide, octanoyl peroxide, cyclohexanone peroxide, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide and the like
  • the peroxide is added in an amount ranging from 500 mg to 2 g per 500 ml of solvent.
  • Said solvent inert to irradiation is appropriately selected from halogen-containing solvents such as chloroform, carbon tetrachloride and the like or aromatic solvents such as benzene, chlorobenzene and the like.
  • the reaction between compound (XIX) and fumaronitrile represented by formula (XVI) is performed by using 1 mole of compound (XIX) and 1-2 moles of fumaronitrile (XVI).
  • the reaction temperature is preferably 70-100°C, and the reaction time is preferably 5-10 hours.
  • polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N,N-diethylformamide, N,N-diethylacetamide and the like are preferable.
  • naphthalocyanine derivative of formula (I) by reacting a naphthalocyanine derivative represented by formula (VII): wherein k, l, m, n, M and Y are as defined in formula (I), with copper (I) thiolate represented by formula (VIII): CuSR1 (VIII) wherein R1 is as defined in formula (I).
  • a naphthalocyanine derivative represented by formula (I) can be obtained by subjecting a compound represented by formula (VII) to a substitution reaction with an excessive quantity of copper (I) thiolate represented by formula (VIII) at an elevated temperature.
  • the reaction temperature is preferably 80-250°C, and the reaction time is preferably 1-30 hours.
  • the solvent of this reaction benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, ⁇ -picoline, quinoline and the like can be used either as a single solvent or as a mixed solvent.
  • the naphthalocyanine derivative (I) can be isolated from reaction mixture and purified by, for example, separating the reaction mixture by column chromatography or thin layer chromatography and thereafter recrystallizing the product.
  • the naphthalocyanine derivative represented by formula (VII) can be obtained by reacting, at an elevated temperature, a naphthalocyanine derivative represented by formula (XX): wherein k, l, m and n, identical or different, independently represent an integer of 0-4, provided that (k+l+m+n) is an integer of 1 or greater, and M represents Si, Ge or Sn, with an excessive quantity of chlorosilane represented by formula (III): (R7)3SiCl (III) or silanol represented by formula (IV): (R8)3SiOH (IV) provided that, in formulas (III) and (IV), R7 and R8 independently represent alkyl group, aryl group, alkoxyl group or aryloxyl group, or an alcohol represented by formula (V): R9OH (V) wherein R9 represents alkyl group or aryl group, or a compound represented by formula (VI): R10CO ⁇ X (VI) wherein R10 represents alkyl group and
  • the reaction temperature is preferably 80-250°C, and the reaction time is preferably 30 minutes to 10 hours.
  • This reaction is preferably carried out either in the absence of solvent or in a solvent such as benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, ⁇ -picoline, quinoline or the like, optionally in the presence of an aliphatic amine such as triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine or the like.
  • a solvent such as benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, tetralin, pyridine, ⁇ -picoline, quino
  • the naphthalocyanine represented by formula (VII) can be isolated from the reaction mixture and purified by, for example, separating the reaction mixture by chromatography and thereafter recrystallizing the product.
  • the naphthalocyanine derivative represented by formula (XX) can be obtained by treating a naphthalocyanine derivative represented by formula (XXI): wherein k, l, m and n, identical or different, independently represent an integer of 0-4, provided that (k+l+m+n) is an integer of 1 or greater, M represents Si, Ge or Sn, and X represents halogen atom, provided that the two symbols X may be identical or different, in concentrated sulfuric acid at room temperature for 1-10 hours, and thereafter heating it under reflux in concentrated aqueous ammonia for 30 minutes to 10 hours or by heating it under reflux in pyridine/water, pyridine/aqueous ammonia, methanol/aqueous ammonia, ethanol aqueous ammonia or propanol/aqueous ammonia for a period of 30 minutes to 10 hours.
  • the naphthalocyanine derivative represented by formula (XXI) can be obtained by reacting, at an elevated temperature, one mole of bromo-1,3-diiminobenz-(f)isoindoline represented by formula (XXII): wherein n represents an integer of 1-4, with 1-100 moles of a metal halide represented by formula (XII): MX p (XII) wherein X represents halogen atom, p is a positive integer representing the number of X linked to metal M, and M represents Si, Ge or Sn.
  • the reaction temperature is preferably 150-300°C, and the reaction time is preferably 30 minutes to 10 hours.
  • the reaction may be carried out either in the absence of solvent or in a solvent such as urea, tetralin, quinoline, 1-chloronaphthalene, 1-bromonaphthalene, trimethylbenzene, dichlorobenzene, trichlorobenzene or the like.
  • This reaction is preferably carried out in the presence of an amine.
  • the amines usable for this purpose include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine and the like.
  • SiCl4, SiBr4, SiI4, GeCl4, GeBr4, SnCl2, SnI2 and the like can be referred to.
  • the bromo-1,3-diiminobenz(f)isoindoline represented by formula (XII) can be obtained by heating, under reflux, bromo-2,3-dicyanonaphthalene represented by formula (XVII): wherein n represents an integer of 1-4, in methanol in the presence of sodium methoxide catalyst for 1-10 hours, while bubbling ammonia gas.
  • an optical recording medium can be obtained by forming a recording film layer composed mainly of a naphthalocyanine derivative represented by formula (I) on a substrate surface.
  • a recording layer composed mainly of naphthalocyanine derivative of formula (I) is provided on a substrate. If desired, other layers such as under layer, protecting layer and the like can also be provided.
  • the substrate material used in this invention is that known to specialists in the art, and it may be transparent or opaque to the used laser beams.
  • the substrate When reading and writing is to be carried out with laser beams from the side of substrate, however, the substrate must be transparent to the laser beams.
  • writing or reading is carried out from the other side, i.e. from the side of recording layer, it is unnecessary to use a substrate transparent to the laser beams.
  • the materials used as the substrate include inorganic materials such as glass, quartz, mica, ceramics, plate or foil of metal and the like and plate of organic polymeric materials such as paper, polycarbonate, polyester, cellulose acetate, nitrocellulose, polyethylene, polypropylene, polyvinyl chloride, vinylidene chloride copolymers, polyamide, polystyrene, polymethyl methacrylate, methyl methacrylate copolymers and the like, though these materials are not limitative.
  • a support made of an organic polymer having a low heat conductivity is preferable because of small heat loss and high sensitivity at the time of recording.
  • a guide channel constituted of concavity and convexity may be provided on the substrate, if desired.
  • an underlayer film may also be provided on the substrate.
  • An optical recording medium wherein there is formed a recording film layer composed mainly of a naphthalocyanine derivative of formula (I) wherein M is Si or Ge is preferable in this invention.
  • An optical recording medium wherein there is formed a recording film layer composed mainly of a naphthalocyanine derivative of formula (I) wherein k, l, m and n all represent a number of 1 is preferable in this invention.
  • An optical recording medium wherein there is formed a recording film layer composed mainly of a naphthalocyanine derivative of formula (I) wherein the two symbols Y both represent a trialkylsiloxyl group is preferable in this invention.
  • An optical recording medium wherein there is formed a recording film layer composed mainly of a naphthalocyanine derivative of formula (I) wherein, in the group R1, x is a number of 1-5 is preferable in this invention.
  • An optical recording medium wherein there is formed a recording film layer composed mainly of a naphthalocyanine derivative of formula (I) wherein R2 and R3 represent H is preferable in this invention.
  • An optical recording medium wherein there is formed a recording film layer composed mainly of a naphthalocyanine derivative of formula (I) wherein R4, R5 and R6 represent straight-chain alkyl groups is preferable in this invention.
  • the above-mentioned optical recording medium can be produced by forming a recording film layer on a substrate surface by the use of a solution prepared by dissolving a naphthalocyanine derivative of formula (I) as a main component into an organic solvent.
  • Said organic solvent is selected from the above-mentioned aromatic, halogen-containing, ether type, ketone type and saturated hydrocarbon type solvents capable of dissolving the naphthalocyanine derivative of formula (I), and it may be any of single solvent and solvent mixture. Preferably, however, a solvent not attacking the used substrate should be used.
  • a dye is dissolved into the solvent, and the resulting solution is formed into a film by spraying, roller coating, spin coating or dipping.
  • a binder such as polymer binder and the like, a stabilizer, etc. may be added if desired.
  • Non-limitative examples of said binder include polyimide resin, polyamide resin, polystyrene resin, acrylic resin and the like.
  • the material for forming the recording layer is a single material or a combination of two or more materials.
  • the structure may be any of laminated structure and single layer structure composed of a mixture of materials.
  • the recording layer preferably has a film thickness of 50 to 10,000 angstroms, and particularly 100 to 5,000 angstroms.
  • a reflected light is often used.
  • a metallic layer exhibiting a high reflectance may be provided on the surface of the recording layer existing in the other side of substrate as a means for enhancing contrast.
  • a metallic layer exhibiting a high reflectance may be provided between the substrate and recording layer.
  • the metal exhibiting a high reflectance Al, Cr, Au, Pt, Sn and the like can be used. These films can be formed by the well known film-forming techniques such as vacuum vapor deposition, sputtering, plasma vapor deposition, etc. Thickness of the film is in the range of 100 to 10,000 angstroms.
  • the naphthalocyanine Since the naphthalocyanine has a high reflectance in itself, it is not particularly necessary to provide a metallic reflecting layer.
  • a protecting layer may be provided in order to improve stability and protection. Further, a layer for decreasing surface reflectance and thereby increasing sensitivity may also be provided.
  • the material used for forming such protecting layers polyvinylidene chloride, polyvinyl chloride, vinylidene chloride-acrylonitrile copolymer, polyvinyl acetate, polyimide, polymethyl methacrylate, polystyrene, polyisoprene, polybutadiene, polyurethane, polyvinyl butyral, fluorinated rubber, polyester, epoxy resin, silicone resin, cellulose acetate and the like can be referred to. These materials may be used either as single material or as a blended mixture.
  • the protecting layer may be formed into a superposed double layer structure.
  • the above-mentioned materials for forming protective layer can be used either by dissolving them into an appropriate solvent and coating the solution or by forming them into a thin film and laminating the film. Thickness of such protecting layer is adjusted to 0.1 to 10 microns, and preferably 0.1 to 2 microns.
  • a process for producing an optical recording medium by the use of a naphthalocyanine derivative of formula (I) wherein M is Si or Ge is preferable in this invention.
  • a process for producing an optical recording medium by the use of a naphthalocyanine derivative of formula (I) wherein k, l, m and n all represent a number of 1 is preferable in this invention.
  • a process for producing an optical recording medium by the use of a naphthalocyanine derivative of formula (I) wherein the two symbols Y both represent a trialkylsiloxyl group is preferable in this invention.
  • a process for producing an optical recording medium by the use of a naphthalocyanine derivative of formula (I) wherein, in the group R1, x is a number of 1-5 is preferable in this invention.
  • a process for producing an optical recording medium by the use of a naphthalocyanine derivative of formula (I) wherein R2 and R3 represent H is preferable in this invention.
  • a process for producing an optical recording medium by the use of a naphthalocyanine derivative of formula (I) wherein R4, R5 and R6 represent straight-chain alkyl groups is preferable in this invention.
  • 6-bromo-2,3-dicyanonaphthalene Under nitrogen, 44.1 g (0.17 mol) of 6-bromo-2,3-dicyanonaphthalene was added to a solution of sodium methoxide in methanol prepared by adding 1.92 g (84 mmols) of metallic sodium in 5 times to 270 ml of absolute methanol, and anhydrous ammonia gas was slowly bubbled into the resulting mixture with sufficient mixing at room temperature for about 1 hour. The mixture was refluxed for about 3 hours, while bubbling therethrough anhydrous ammonia gas. After cooling, the yellow solid precipitated was collected by filtration, sufficiently washed with methanol and dried under reduced pressure to obtain 45 g of 6-bromo-1,3-diiminobenz[f]isoindoline as a yellow solid.
  • dichlorosilicon-tetrabromonaphthalocyanine (the formula (XXI): M is Si; X is a chlorine atom; and k, l, m, and n are 1, respectively) as a dark-green solid.
  • This dichlorosilicon-tetrabromonaphthalocyanine was used in the subsequent reaction without further purification.
  • IR spectrum of dichlorosilicon-tetrabromonaphthalocyanine is shown in Fig. 5. Its electronic spectrum is shown in Fig. 6.
  • dihydroxysilicon-tetrabromonaphthalocyanine (the formula (XX): M is Si and k, l, m, and n are 1, respectively) as a dark-green solid.
  • This dihydroxysilicon-tetrabromonaphthalocyanine was used in the subsequent reaction without further purification.
  • IR spectrum of dihydroxysilicon-tetrabromonaphthalocyanine is shown in Fig. 7. Its electronic spectrum is shown in Fig. 8.
  • the dark-green crystals were confirmed to be bis(tri-n-butylsiloxy)silicon-tetrabromonaphthalocyanine (the formula (VII): M is Si; k, l, m and n are 1, respectively; and each Y is a tri-n-butylsiloxyl group) from the following analysis results:
  • the dark-green crystals were confirmed to be bis(tri-n-hexylsiloxy)silicon-tetrabromonaphthalocyanine (the formula (VII): M is Si; k, l, m, and n are 1, respectively; and each Y is a tri-n-hexylsiloxyl group) from the following analysis results:
  • the dark-green crystals were confirmed to be bis(triethylsiloxy)-silicon-tetrabromonaphthalocyanine (the formula (VII): M is Si; k, l, m and n are 1, respectively; and each Y is a triethylsiloxyl group) from the following analysis results:
  • Impurities present in this product were removed by silica gel flush column chromatography (toluene/cyclohexane elution), and the crystal obtained was recrystallized from toluene/methanol mixture to obtain 620 mg of a green colored crystalline product.
  • an organic film having a thickness of about 700 angstroms was formed by spin-coating a solution consisting of 1 part by weight of bis(tri-n-butylsiloxy)silicon-tetra(trimethylsilylmethylthio)naphthalocyanine (Compound (8)) and 99 parts by weight of cyclohexane and drying it at about 80°C for 15 minutes. Absorption spectrum, transmission spectrum and 5° specular reflection spectrum of the organic film of this compound are shown in Fig. 37, 38 and 39, respectively. It is understandable from these spectra that this compound exhibits a high light-absorbing ability and a high reflectance (ca. 60%) in the semiconductor laser region (780-830 nm).
  • Compound (8) bis(tri-n-butylsiloxy)silicon-tetra(trimethylsilylmethylthio)naphthalocyanine
  • an organic film having a thickness of about 700 angstroms was formed by spin-coating a solution consisting of 1 part by weight of bis(tri-n-butylsiloxy)silicon-tetra-(trimethylsilylmethylthio)naphthalocyanine (Compound (8)) and 99 parts by weight of cyclohexane and drying it at about 80°C for 15 minutes. Absorption spectrum, transmission spectrum and 5° specular reflection spectrum of the organic film of this compound formed on polycarbonate substrate are shown in Fig. 40, 41 and 42, respectively. It is understandable from these results that, similarly to the case of glass substrate, a high light-absorbing ability and a high reflectance (ca. 60%) are exhibited by this organic film in the semiconductor laser region (780-830 nm), on polycarbonate substrate, too.
  • Compound (8) bis(tri-n-butylsiloxy)silicon-tetra-(trimethylsilylmethylthio)naphthalocyanine
  • an organic film having a thickness of about 600 angstroms was formed by spin-coating a solution consisting of 1 part by weight of bis(triethylsiloxy)silicon-tetra-(trimethylsilylmethylthio)naphthalocyanine (Compound (16)) and 99 parts by weight of cyclohexane and drying it at about 80°C for 15 minutes. Absorption, transmission and 5° reflection spectra of the organic film of this compound on polycarbonate substrate are shown in Fig. 43, 44 and 45, respectively. It is understandable that an organic film exhibiting a high absorbing ability and a high reflectance (ca. 45%) in the semiconductor laser region (780-830 nm) can be formed.
  • an organic film having a thickness of about 600 angstroms was formed by spin-coating a solution consisting of 1 part by weight of bis(tripropylsiloxy)silicon-tetra(trimethylsilylmethylthio)naphthalocyanine (Compound (9)) and 99 parts by weight of cyclohexane and drying it at about 80°C for 15 minutes. Absorption, transmission and 5° reflection spectra of the organic film of this compound on polycarbonate substrate are shown in Fig. 46, 47 and 48. It is understandable that an organic film exhibiting a high light-absorbing ability and a high reflectance (ca. 55%) in the semiconductor laser region (780-830 nm) can be formed.
  • an organic film was formed by spin coating a solution consisting of 1 part by weight of bis(tri-n-hexylsiloxy)silicon-tetra-(trimethylsilylmethylthio)naphthalocyanine (Compound (13)) and 99 parts by weight of cyclohexane, and drying it at about 80°C for 15 minutes. Absorption, transmission and 5° specular reflection spectra of the organic film of this compound on polycarbonate substrate are shown in Fig. 49, 50 and 51, respectively. It is understandable that an organic film exhibiting a high light-absorbing ability and a high reflectance (ca. 50%) in the semiconductor laser region (780-830 nm) can be formed.
  • Fig. 52 is an electronic spectrum of vanadyltetra(t-butyl)naphthalocyanine synthesized according to the method of Zhurnal Obshchei Khimii, vol. 42, page 696 (1972) in chloroform solution
  • Fig. 53 is its electronic spectrum in benzene solution.
  • the wave shape of absorption changes with the kind of solvent and concentration.
  • the absorption near 800 nm becomes smaller and the absorption near 700 nm becomes greater, as the concentration increases.
  • an organic film of vanadyltetra(t-butyl)naphthalocyanine used in Comparative Example 1 was formed in the same manner as in Example 5 by the use of its solution in 1,1,2-trichloroethane, and transmission spectrum (Fig. 54) and 5° specular reflection spectrum (Fig. 55) of this film were measured.
  • the film did not exhibit high light-absorbing ability nor high reflectance (below 20%) in the semiconductor laser region (780-830 nm).
  • a solution consisting of 1 part by weight of the exemplified naphthalocyanine compound of this invention and 99 parts by weight of solvent was spin-coated on various substrates having a thickness of 1.2 mm and a diameter of 130 mm and different in composition, and dried at about 80°C for 15 minutes to form a recording layer. Thickness of the recording layer was measured by means of Dektak 3030 manufactured by Sloan Co. Each of the recording media thus prepared was placed on a turn table and rotated at a speed of 900 rpm.
  • a laser beam was projected from the substrate side by the use of an optical head equipped with a semiconductor laser having an oscillating wavelength of 830 nm and an output of 6 mW on the substrate surface, so that the laser beams were concentrated into the recording layer through the substrate, and pulse signals of 2MHz were recorded in the zone of 40 to 60 mm from the center. Then, the recorded signals were reproduced on the same apparatus as above, while adjusting the output of semiconductor laser to 1.0 mW as measured on the substrate surface, and CN ratio (carrier to noise ratio) was evalulated.
  • the results are shown in the following table.
  • the exemplified compounds shown in the table could form a recording layer exhibiting quite excellent recording and reproducing characteristics on various substrates.
  • PC signifies polycarbonate substrate
  • PMMA does polymethyl methacrylate substrate
  • PMMA2P does polymethyl methacrylate 2P substrate.
  • OVNc(t-C4H9)4 was spin-coated as a chloroform solution in the same manner as in Example 10 to form a recording layer. Thickness of this recording layer was about 1,000 angstroms. The recording material thus obtained was recorded and reproduced in the same manner as in Example 10. As a result, CN ratio (carrier to noise ratio: CNR) was 39 dB, and writing-in and reading-out of signals could not be performed satisfactorily.
  • CNR carrier to noise ratio
  • Naphthalocyanine derivative (8) exemplified above was dissolved into cyclohexane to prepare a 1% solution. Using this solution, a recording film layer having a thickness of 700 angstroms was prepared on a polycarbonate substrate having a thickness of 1.2 mm by spin coating method. The recording medium thus obtained was irradiated with semiconductor laser having a wave-length of 830 nm from the side of substrate, and its recording characteristics were evaluated. As a result, recording was possible at a beam diameter of 1.6 microns, a line speed of 6.0 m/second, 7.0 mW.
  • a recording film layer having a thickness of 500 angstroms was prepared by spin coating cyanine type dye NK-2905 (manufactured by Nippon Kanko Shikiso Kenkyosho) dissolved in dichlorethane onto a glass substrate.
  • This recording medium was irradiated with laser beams in the same manner as in Example 11. As a result, recording could be performed at 4.8 mW.
  • reflectance began to decrease from about an irradiation number of about 4 x 104, and CN ratio decreased to 70% of the initial value after the irradiation number reached 106.
  • a recording film layer having a thickness of 700 angstroms was prepared on a polycarbonate substrate by roller-coating naphthalocyanine derivative (9) dissolved in cyclohexane.
  • the recording medium thus obtained was irradiated with semiconductor laser having a wavelength of 830 nm from the substrate side, and its recording characteristics were evaluated. As a result, recording could be performed at a beam diameter of 1.6 microns, at a line speed of 6.5 m/second, at 6.1 mW.
  • stability to reproduction deterioration was evaluated by repeatedly irradiating a reading light of 1.0 mW. As a result, no change in CN ratio was observed even if the irradiation was repeated 106 times.
  • a recording film layer having a thickness of 720 angstroms was prepared by spin coating naphthalocyanine derivative (10) dissolved in cyclohexane.
  • the recording medium thus obtained was irradiated with laser beams in the same manner as in Example 12. As a result, recording could be performed at 6.3 mW. In the evaluation of stability to reproduction deterioration, no change in CN ratio was observed even if irradiation was repeated 106 times.
  • a recording film layer was formed by spin coating a 2:1 mixture of naphthalocyanine derivative (8) and polystyrene dissolved in toluene. Thickness of the recording film layer was 1,300 angstroms.
  • a recording film layer having a thickness of 700 angstroms was formed by spin coating naphthalocyanine derivative (11) dissolved in cyclohexane.
  • the recording medium thus obtained was irradiated with semiconductor laser having a wavelength of 830 nm from the substrate side, and the recording characteristics were evaluated. As a result, recording could be performed at a beam diameter of 1.6 microns, at a line speed of 7.5 m/second, at 7.2 mW.
  • a reading light of 0.9 mW was repeatedly irradiated. As a result, no change in CN ratio was observed even if the irradiation was repeated 106 times.
  • a recording film layer having a thickness of 700 angstroms was formed by spin coating naphthalocyanine derivative (13) dissolved in cyclohexane.
  • the recording medium thus obtained was irradiated with laser beams in the same manner as in Example 12. As a result, recording could be performed at 6 mW. In the evaluation of stability to reproduction deterioration, no change in CN ratio was observed even if the irradiation was repeated 106 times.
  • a recording film layer having a thickness of 500 angstroms was formed by spin coating cyanine dye NK-2837 (manufactured by Nippon Kanko Shikiso Kenkyusho) dissolved in dichlorethane.
  • the recording medium thus obtained was irradiated with laser beams in the same manner as in Example 12. As a result, recording could be performed at 5.2 mW.
  • CN ratio began to decrease when irradiation number reached about 5 x 104, CN ratio decreased 70% of the initial value after the irradiation number had reached 106.
  • a recording film layer having a thickness of 600 angstroms was formed by spin coating naphthalocyanine derivative (15) dissolved in cyclohexane.
  • the recording medium thus obtained was irradiated with laser beams in the same manner as in Example 12. As the recording could be performed at 4 mW. In the evaluation of stability to reproduction deterioration, no change in CN ratio was observed even if the irradiation was repeated 106 times.
  • a recording film layer having a thickness of 670 angstroms was formed by spin coating naphthalocyanine derivative (16) dissolved in cyclohexane.
  • the recording medium thus obtained was irradiated with laser beams in the same manner as in Example 12. As a result, recording could be performed at 4.9 mW. In the evaluation of stability to reproduction deterioration, no change in CN ratio was observed even if the irradiation was repeated 106 times.
  • a recording film layer having a thickness of 710 angstroms was formed by spin coating naphthalocyanine derivative (17) dissolved in toluene.
  • the recording medium thus obtained was irradiated with laser beams in the same manner as in Example 12. As a result, recording could be performed at 4.2 mW. In the evaluation of stability to reproduction deterioration, no change in CN ratio was observed even if the irradiation was repeated 106 times.
  • a recording film layer having a thickness of 710 angstroms was formed by spin coating naphthalocyanine derivative (19) dissolved in cyclohexane.
  • the recording medium thus prepared was evaluated at a line speed of 5 m/second in the same manner as in Example 12. As a result, recording could be performed at 6.8 mW. In the evaluation of reproduction deterioration, no change in CN ratio was observed even if the irradiation was repeated 106 times.
  • a recording film layer having a thickness of 900 angstroms was formed by coating a 2:1 mixture of naphthalocyanine derivative (20) and polystyrene dissolved in methyl ethyl ketone. It was evaluated in the same manner as in Example 12. As a result, the recording sensitivity was 4.8 mW and the reproduction deterioration was 106 or above.
  • Naphthalocyanine derivative (21) was dissolved into butanol to prepare a 0.9% by weight solution. Then, a recording layer having a thickness of 600 angstroms was formed on a glass substrate having a thickness of 1.2 mm by spin coating process. The recording medium thus obtained was irradiated with semiconductor laser having a wavelength of 830 nm from the glass substrate side, and its recording characteristics were evaluated. As a result, recording could be performed at a 1/e2 beam diameter of 1.6 microns, at a line speed of 7.6 m/second, at 6.9 mW. On the other hand, in the evaluation of reproduction deterioration, a reading light of 1.0 mW was repeatedly projected. No change in CN ratio was observed even if the irradiation was repeated 106 times.
  • Naphthalocyanine derivative (24) was dissolved into butanol to prepare a 1.0% (by weight) solution.
  • a recording layer having a thickness of 650 angstroms was formed on a glass substrate having a thickness of 1.2 mm by spin coating process.
  • the recording medium thus obtained was irradiated with semiconductor laser beams having a wavelength of 830 nm from the substrate side, and its recording characteristics were evaluated. As a result, recording could be performed at a 1/e2 beam diameter of 1.6 microns, at a line speed of 7.6 m/second, at 8.6 mW.
  • a reading light of 1.0 mW was repeatedly irradiated. As a result, no change in CN ratio was observed even if the irradiation was repeated 106 times.
  • a recording layer having a thickness of 800 angstroms was formed by spin coating a 2:1 mixture of naphthalocyanine derivative (25) and polystyrene dissolved in 1,1,2-trichloroethane.
  • the recording medium thus prepared was irradiated with semiconductor laser having a wavelength of 830 nm from the side of substrate, and its recording characteristics were evaluated. As a result, recording could be performed at a line speed of 8 m/second, at 6 mW.
  • a reading light of 0.9 mW was repeatedly irradiated, no change in CN ratio was observed even if the irradiation was repeated 106 times.
  • a recording layer having a thickness of about 700 angstroms was formed by spin-coating a solution consisting of 1 part by weight of naphthalocyanine derivative (8) and 99 parts by weight of cyclohexane.
  • the optical recording medium thus prepared was allowed to stand under a high temperature-high humidity condition (80°C, 90% RH) and its reflectance was measured. As shown in Fig. 57, it retained 95% of the initial reflectance. The change in reflectance in the lapse of time was expressed by percentage to initial reflectance, taking the initial reflectance as unity.
  • a recording layer was formed by spin-coating cyanine dye NK-2905 (manufactured by Nippon Kanko Shikiso Kenkyusho) dissolved in dichloroethane.
  • the optical recording medium thus prepared was allowed to stand under a high temperature-high humidity condition (80°C, 90% RH) for 3,000 hours, and its reflectance was measured. As shown in Fig. 58, the reflectance began a rapid decrease when about 500 hours had passed, demonstrating durability of the recording medium was not good. Further, CNR retention was evaluated in the same manner as in Example 26, under accelerated environmental conditions. As a result, CNR decreased to 70% of the initial value.
  • An optical recording medium prepared in the same manner as in Example 25 was allowed to stand under a high temperature-high humidity condition (80°C, 90% RH), and CNR was measured after 3,000 hours had passed. As shown in Table 3, a good retention of CNR was observed.
  • the naphthalocyanine derivative of this invention has an excellent solubility in saturated hydrocarbon type solvents. Accordingly, the naphthalocyanine derivative of this invention makes it possible to form a recording layer on the surface of optical disc substrate made of polymethyl methacrylate or polycarbonate easily, without providing any protecting layer on the surface. Further, since the naphthalocyanine derivative of this invention has at least 5, more preferably at least 7 silicon atoms, the amorphous film formed therefrom is excellent in the resistance to reproduction deterioration and amorphous film-retaining performance under the conditions of accelerating environmental test. Further, owing to the use of the naphthalocyanine derivative of this invention exhibiting excellent absorbing and reflecting performances in the semiconductor laser region, the optical recording medium of this invention can use laser beams as an effective electromagnetic energy for recording and reproduction.

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Claims (11)

  1. Naphthalocyaninderivate der Formel (I)
    Figure imgb0043
     worin die Gruppen R¹ gleich oder unterschiedlich sind und je eine Gruppe -(CR²R³)xSiR⁴R⁵R⁶ bedeuten, worin x eine ganze Zahl von 1 bis 30 bedeutet und die Gruppen CR²R³ gleich oder unterschiedlich sind und R², R³, R⁴, R⁵ und R⁶ gleich oder unterschiedlich sind und je Wasserstoff, Halogen, Alkyl, Alkoxy, Aryl oder Aryloxy bedeuten;
    k, l, m und n gleich oder unterschiedlich sind und je eine ganze Zahl von 0 bis 4 bedeuten, mit der Maßgabe, daß (k+l+m+n) 1 oder mehr bedeutet; M Si, Ge oder Sn bedeutet und die Gruppen Y gleich oder unterschiedlich sind und je Aryloxy, Alkoxy, Trialkylsiloxy, Triarylsiloxy, Trialkoxysiloxy oder Acyloxy bedeuten.
  2. Verbindung nach Anspruch 1, worin M Si oder Ge bedeutet.
  3. Verbindung nach Anspruch 1 oder 2, worin jedes von k, l, m und n 1 bedeutet.
  4. Verbindung nach einem der Ansprüche 1 bis 3, worin die beiden Gruppen Y gleich oder unterschiedlich sind und je Trialkylsiloxy bedeuten.
  5. Verbindung nach einem der Ansprüche 1 bis 4, worin R² und R³ beide Wasserstoff bedeuten.
  6. Verbindung nach einem der Ansprüche 1 bis 5, worin x eine Zahl von 1 bis 5 bedeutet.
  7. Verbindung nach einem der Ansprüche 1 bis 6, worin R⁴, R⁵ und R⁶ gleich oder unterschiedlich sind und je Alkyl mit gerader Kette bedeuten.
  8. Verfahren zur Herstellung einer Verbindung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß ein Naphthalocyaninderivat der Formel (II)
    Figure imgb0044
     worin k, l, m, n, R¹ und M die bei der Formel (I) gegebenen Definitionen besitzen, mit einem Chlorsilan der Formel (III)

            (R⁷)₃SiCl   (III)

    worin R⁷ Alkyl, Aryl, Alkoxy oder Aryloxy bedeutet, oder mit einem Silanol der Formel (IV)

            (R⁸)₃SiOH   (IV)

    worin R⁸ Alkyl, Aryl, Alkoxy oder Aryloxy bedeutet, oder mit einem Alkohol der Formel (V)

            R⁹OH   (V)

    worin R⁹ Alkyl oder Aryl bedeutet, oder mit einer Verbindung der Formel (VI)

            R¹⁰CO.X   (VI)

    worin R¹⁰ Alkyl und X Halogen, Hydroxy oder Acyloxy bedeuten, umgesetzt wird.
  9. Verfahren zur Herstellung einer Verbindung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß ein Naphthalocyaninderivat der Formel (VII)
    Figure imgb0045
     worin k, l, m, n, M und Y die bei der Formel (I) gegebenen Bedeutungen besitzen, mit einem Kupfer(I)-thiolat der Formel (VIII)

            CuSR¹   (VIII)

    worin R¹ die bei der Formel (I) gegebene Definition besitzt, umgesetzt wird.
  10. Optisches Aufzeichnungsmedium, dadurch gekennzeichnet, daß es eine Aufzeichnungsfilmschicht, die hauptsächlich aus einer Verbindung nach einem der Ansprüche 1 bis 7 zusammengesetzt ist oder die nach einem der Ansprüche 8 oder 9 auf einem Substrat gebildet worden ist, umfaßt.
  11. Verfahren zur Herstellung eines optischen Aufzeichnungsmediums, dadurch gekennzeichnet, daß eine Verbindung, die nach irgendeinem der Ansprüche 1 bis 7 oder nach einem der Ansprüche 8 oder 9 hergestellt worden ist, als Hauptkomponente in einem organischen Lösungsmittel gelöst wird und daß auf einer Substratoberfläche unter Verwendung der so hergestellten Lösung eine Aufzeichnungsfilmschicht gebildet wird.
EP90300185A 1989-01-11 1990-01-08 Naphthalocyaninderivate, deren Herstellung, optisches Wiedergabe-Medium mit solchen Verbindungen und dessen Herstellung Expired - Lifetime EP0378336B1 (de)

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US7314705B2 (en) 2003-09-05 2008-01-01 Hewlett-Packard Development Company, L.P. Compositions, systems, and methods for imaging

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JPH07507074A (ja) * 1991-11-08 1995-08-03 イーストマン ケミカル カンパニー 近赤外発螢光団を有する熱可塑性材料の標識方法
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Also Published As

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US5039600A (en) 1991-08-13
JPH02283768A (ja) 1990-11-21
DE69004811T2 (de) 1994-04-14
JPH0721119B2 (ja) 1995-03-08
DE69004811D1 (de) 1994-01-13
EP0378336A1 (de) 1990-07-18
US5110968A (en) 1992-05-05

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